CN101679741A - The article of rub resistance and wearing and tearing - Google Patents
The article of rub resistance and wearing and tearing Download PDFInfo
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- CN101679741A CN101679741A CN200880019402.9A CN200880019402A CN101679741A CN 101679741 A CN101679741 A CN 101679741A CN 200880019402 A CN200880019402 A CN 200880019402A CN 101679741 A CN101679741 A CN 101679741A
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- ether ketone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
- C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
A kind of article, comprise at least one part with an area supported, described part be by comprise at least a poly-(aryl ether ketone) (P1) and at least a poly-((arylene sulfide)) polymer composition (P2) constitute, wherein: described poly-(aryl ether ketone) (P1) and described poly-((arylene sulfide)) combined weight (P2) be to be lower than 0.75 based on the gross weight of described polymer composition, and described poly-((arylene sulfide)) (P2) is included between 0.2 and 0.8 with described (aryl ether ketone) weight ratio (P1) of gathering.
Description
The cross reference of related application
This application requires the U.S. Provisional Application submitted on April 23rd, 2007 number 60/913,395 and the right of priority of the U.S. Provisional Application submitted on May 4th, 2007 number 60/915,973, and the full content of these two applications all is combined in this by reference.
Invention field
The present invention relates to a kind of article, these article comprise at least one part with an area supported, and these article are used particularly useful to friction and wear.
In addition, the invention still further relates to a kind of polymer composition, it is suitable for making described article especially goodly.
Background of invention
The Science and Technology that the field of tribology relates to friction, lubricates and wear and tear.Tribology is defined by the surperficial subject that influences each other in relative movement.Tribology comprises the friction relevant with these surfaces, wearing and tearing and lubricated research generally.Tribological material is characterized by different parameters usually, and except other things, these parameters comprise: wear intensity, bear the load and ability, frictional coefficient, rigidity and the dimensional stability of speed.A kind of " wear intensity " of material is meant the amount of the material of removing from this area supported that causes for the relative movement with the interactional surface of this area supported owing to an area supported generally.A kind of wear intensity of material is reported as " wear factor " usually, and it is proved, and the correlated measure as material property is very reliable under identical working conditions.
Seeking and having the article of an area supported that combines improved tribology (i.e. the friction and wear of interactive surfaces in relative movement) and machine capability to be used for multiple friction and wear application for some industrial sectors.
The tribological material of plastics is normally used in the supporting application.The prior art polymers composition that is used for the friction and wear application comprises that generally the engineering polymers class of miocrystalline and/or amorphous phase or their mixture [for example gather (ether ketone) (PEK), gather (ether ether ketone) (PEEK), gather (tetrafluoroethylene) (PTFE), polycarbonate-based (PC), liquid crystal polyester class (LCP), the acetal copolymer class, aliphatic or aromatic polyamide-based, polysulfones (PSF), gather (ether sulfone) (PES), gather (benzene sulfone) (PPSF), gather (ether ether sulfone) (PEES), polyamideimides (PAI), polyimide (PI)].
Research constantly makes great efforts to replace existing material to improve tribological property with the prescription by optimizing existing matrix material and/or by using up brand-new polymer composition.Because the complicacy of tribology phenomenon, such research are still experimental mostly.
Plastic supporting member is normally made in a kind of polymer materials by additive kind (such as weighting agent, strongthener and/or solid lubricant) incorporated into.On the tribology of this type of material and other property characteristic depend on employed concrete matrix material and with the concrete additive of this matrix material preparation.Yet, the experience of prior art taught the effect of in a kind of polymeric matrix, incorporating one or more additives into be not be easily prediction and even may unexpected fully (especially cross over the different operating condition of wide region: temperature, sliding velocity, pressure, additive load) and this type of effect depend on the character of this polymeric matrix very doughtily.For example, Graphite Powder 99 added caused the polymer composition that significantly descends than The friction coefficient temperature among the PAI, cause frictional coefficient to cross over the wide almost constant polymer composition of temperature range among the PTFE yet same additives added.Sometimes, the expection additive that is used for improving a kind of tribological property level of polymer composition may have deleterious side effect.For example, particulate weighting agent and glass fibre weighting agent (carrying out blend to improve its wear resistance with relative soft PTFE) pottery or metal have increased the dry sliding friction coefficient and the counterface that worn and torn concurrently.
Some poly-(aryl ether ketones) are crystalline and the excellent combination that shows following characteristic, i.e. You Yi heat and stability to hydrolysis, high intensity and toughness, excellent wear-resistant and abradability and the solvent resistance of excellence.Therefore, requiring to have practicality under the high performance situation by the poly-molded article of (aryl ether ketone) class.Particularly, nowadays poly-(ether ether ketone) (PEEK) is widely used in preparing and is intended to be used for the friction and wear preparation that wear-resistant type is used.Yet PEEK is a kind of very expensive resin, and on the market for the benefit of most of thermotolerances that PEEK friction and wear preparation is provided and wear resistance but there is the material of the cost of reduction to have a kind of needs.
US 4,684,699 have disclosed a kind of alloy, this alloy comprise from poly-((arylene sulfide)) of about 2wt.% to 98wt.% and from the crystallization poly-(aryl ether ketone) of 98wt.% to 2wt.% but do not mention about any article or about any friction and wear of this polymer compositions and using with the area supported that comprises this polymer compositions.
Therefore, there are a kind of needs in article with area supported (use for friction and wear particularly useful), these article comprise the most ofs heat-resisting and wear resistance of poly-(aryl ether ketone) friction and wear composition that prior art can be provided but have reduction cost gather (aryl ether ketone) composition.
Summary of the invention
Unexpectedly find, a kind of article satisfy these expectations, these article comprise at least one part that has an area supported, described part be by comprise at least a poly-(aryl ether ketone) (P1) and at least a poly-((arylene sulfide)) polymer composition (P2) constitute, wherein:
-this poly-(aryl ether ketone) based on the gross weight of this polymer composition, is to be lower than 0.75 (P1) and poly-((arylene sulfide)) combined weight (P2), and
-poly-((arylene sulfide)) (P2) with should gather (aryl ether ketone) weight ratio (P1) and be included between 0.2 and 0.8.
In a preferred embodiment, this polymer composition further comprises at least a antifriction additive.When being 0.30, the weight ratio of this antifriction additive and polymer composition obtained good result at least.
According to poly-((arylene sulfide)) of above qualification (P2) with poly-(aryl ether ketone) weight ratio (promptly between 0.2 and 0.8) (P1) by will gather (aryl ether ketone) (P1) with poly-((arylene sulfide)) (P2) carry out blend and by will gather (aryl ether ketone) (P1) with gather ((arylene sulfide)) combined weight (P2) and be reduced to gross weight based on this polymer composition less than 0.75, polymeric constituent in the part with an area supported (P1) and cost (P2) reduce significantly, and this causes the article that the cost magnetism is arranged in this invention.Also unexpectedly find, when the polymer composition that constitutes this part further comprises a kind of antifriction additive, the wear resisting property of the part that is made of this polymer composition is maintained at and is made of the same polymeric compositions but does not contain the substantially the same level of poly-((arylene sulfide)) part (P2), described poly-((arylene sulfide)) (P2) weight weight ground (P1) is replaced by described poly-(aryl ether ketone) fully.
Another aspect of the present invention is meant at the polymer composition itself that constitutes above-mentioned part.Therefore, the invention still further relates to a kind of polymer composition, this polymer composition is suitable for making an a kind of part that has an area supported of article especially goodly, described polymer composition comprise at least a poly-(aryl ether ketone) (P1) and at least a poly-((arylene sulfide)) (P2), wherein:
-this poly-(aryl ether ketone) based on the gross weight of this polymer composition, is to be lower than 0.75 (P1) and poly-((arylene sulfide)) combined weight (P2), and
-poly-((arylene sulfide)) (P2) with should gather (aryl ether ketone) weight ratio (P1) and be included between 0.2 and 0.8.
In a preferred embodiment, polymer composition of the present invention further comprises at least a antifriction additive.When being 0.30, the weight ratio of this antifriction additive and polymer composition obtained good result at least.
Polymer composition
According to previous mentioned, polymer composition according to the present invention comprise at least a poly-(aryl ether ketone) (P1) and at least a poly-((arylene sulfide)) (P2).
In polymer composition according to the present invention, this poly-(aryl ether ketone) (P1) gathers ((arylene sulfide)) combined weight (P2) with being somebody's turn to do, and based on the gross weight of this polymer composition, is to be lower than 0.75; It is preferably maximum 0.70, is more preferably maximum 0.65 and will be more preferably maximum 0.60.On the other hand, should poly-(aryl ether ketone) (P1) and should poly-((arylene sulfide)) combined weight (P2), based on the gross weight of this polymer composition, normally at least 0.30, preferably at least 0.40, be more preferably at least 0.45 and will be more preferably at least 0.50.
And, in polymer composition according to the present invention, this poly-((arylene sulfide)) (P2) with should gather (aryl ether ketone) weight ratio (P1) and be included between 0.2 and 0.8.Should poly-((arylene sulfide)) (P2) with should poly-(aryl ether ketone) weight ratio (P1) preferably at least 0.25, be more preferably at least 0.3, also to be more preferably at least 0.4 and most preferably be at least 0.45.On the other hand, this poly-((arylene sulfide)) (P2) with should poly-(aryl ether ketone) weight ratio (P1) preferably maximum 0.7, are more preferably at most 0.6, and are more preferably maximum 0.55.
Gather (aryl ether ketone) (P1)
For the purposes of the present invention, term " poly-(aryl ether ketone) " is intended to represent any polymkeric substance, the repeating unit greater than 50wt.% of this polymkeric substance is to comprise that at least one is in the repeating unit of two carbonyl groups between the arylene group (R1), and described repeating unit (R1) has one or more in the following chemical formula:
Wherein:
-Ar is the aromatic group that is selected from a divalence of phenylene, biphenylene or naphthylidene independently,
-X be independently O, C (=O) or a direct key,
-n is an integer of from 0 to 3,
-b, c, d and e are 0 or 1,
-a is an integer of from 1 to 4, and
-preferably, when b was 1, d was 0.
Repeating unit (R1) can particularly be selected from:
And
Preferably, repeating unit (R1) is selected from:
And
Poly-(aryl ether ketone) according to the present invention (P1) preferably is selected from down group, and it constitutes: poly-(ether ether ketone), poly-(ether ketone), poly-(ether ketone ketone) and their mixture.
For the purposes of the present invention, a kind of poly-(ether ketone) is intended to represent that the repeating unit greater than 50wt.% is any polymkeric substance of repeating unit (R1) with chemical formula (VI).
For the purposes of the present invention, a kind of poly-(ether ether ketone) is intended to represent that the repeating unit greater than 50wt.% is any polymkeric substance of repeating unit (R1) with chemical formula (VII).
For the purposes of the present invention, a kind of poly-(ether ketone ketone) is intended to represent that the repeating unit greater than 50wt.% is any polymkeric substance of repeating unit (R1) with chemical formula (IX).
More preferably, repeating unit (R1) is:
Preferred poly-(aryl ether ketone) (P1) be repeating unit (R1) greater than 70wt.% and more preferably greater than the repeating unit of 85wt.%.Also more preferably, poly-(aryl ether ketone) whole basically repeating unit (P1) all is repeating unit (R1).Most preferably, poly-(aryl ether ketone) whole repeating units (P1) all are repeating unit (R1).
When poly-(aryl ether ketone) is a kind of poly-(ether ether ketone) homopolymer (P1), promptly whole basically (if not whole words) repeating units is to have obtained excellent result when having a kind of polymkeric substance of chemical formula (VII).From Victrex Manufacturing Ltd.'s
150P and
450P PEEK and from Solvay Advanced Polymers, L.L.C.'s
With
PEEK is the example of poly-(ether ether ketone) homopolymer.
Polymkeric substance (P1) is with respect to the gravimetric value of the gross weight of this polymer composition 20wt.% at least preferably, and is more preferably 30wt.% at least; In addition, polymkeric substance (P1) is more preferably maximum 60wt.% with respect to the preferably maximum 70wt.% of gravimetric value of the gross weight of this polymer composition, also is more preferably maximum 50wt.%, and most preferably is maximum 40wt.%.
Gather ((arylene sulfide)) (P2)
For the purposes of the present invention, poly-((arylene sulfide)) (P2) is intended to represent that a kind of polymkeric substance, the repeating unit greater than 50wt.% of this polymkeric substance are the repeating units (R2) with chemical formula universal below one or more:
-Ar-S-????????????????????????????????????????????????(R2)
Wherein the Ar group is represented the arylene group that can choose replacement wantonly, and such as a phenylene or a naphthylidene group, it is connected to separately on two sulphur atoms and via a direct C-S key by its two ends and forms sulfide group.Preferred repeating unit Ar be can choose wantonly replacement to phenylene (form repeating unit (R2) as
) and can choose wantonly replacement metaphenylene (form repeating unit (R2) as
).
The arylene group Ar that can randomly replace can be unsubstituted, and this often is preferred.
In certain embodiments, this arylene group Ar that can choose replacement wantonly can be replaced by one or more substituted radical, and these substituted radicals include but not limited to halogen atom, C
1-C
12Alkyl, C
7-C
24Alkaryl, C
7-C
24Aralkyl, C
6-C
18Aryl, C
1-C
12Alkoxy base and C
6-C
18Aryloxy group, and replace or unsubstituted arylene sulfide ether group itself, their arylene group also is connected to two sulphur atoms by their two ends and separately via a direct C-S key formation sulfide group, for example in the following formula:
Produce ramose thus, until crosslinked polymer chain.
Should poly-((arylene sulfide)) preferably comprise greater than 70wt.%, more preferably greater than 80wt.% and will be more preferably greater than the repeating unit (R2) of 90wt.%.Most preferably, it does not contain the repeating unit except that (R2).
A kind of preferred poly-((arylene sulfide)) is poly-(phenylene sulfide), and promptly a kind of polymkeric substance, the repeating unit greater than 50wt.% of this polymkeric substance are the repeating units with following universal one kind of multiple chemical formulas:
-pPh-S-????????????????????????????????????????????(R3)
Wherein the pPh group represent one can choose wantonly replacement to phenylene group, be connected to two sulphur atoms separately and form sulfide group by its two ends via a direct C-S key.
PPh can be unsubstituted, and this often is preferred.
In certain embodiments, pPh can be replaced by one or more substituted radical, and these substituted radicals include but not limited to halogen atom, C
1-C
12Alkyl (form replace unit (R3)) as
This polyphenylene sulfide preferably comprises greater than 70wt.%, more preferably greater than 80wt.% and will be more preferably greater than the repeating unit (R3) of 90wt.%.
Should gather ((arylene sulfide)), particularly poly-(phenylene sulfide) can further comprise the repeating unit except that (R2); The nonrestrictive example of the repeating unit except that (R2) is to pass through Na
2The reaction of S and the dihalide compound with general formula Cl-Ar °-D-Ar-Cl is by removing those repeating units that the dechlorination atom forms from this dihalide compound:
Na
2S+Cl-Ar °-D-Ar °-Cl →-Ar °-D-Ar °-S-repeating unit (R4)
Wherein Ar ° be a kind of arylene group of choosing replacement wantonly and D can be except that thioether (S-) or divided by the two end capped diradicals of thioether (S-D '-S-, wherein D ' can be any diradical) outside any diradical.
Two fragment-Ar °-S-of repeating unit (R4) are different from repeating unit (R2), difference is to choose wantonly group Ar ° of replacement and is not connected to two sulphur atoms separately and forms sulfide group via a direct C-S key by its two ends, at least one end of each arylene group Ar ° with as the D of above definition link to each other.
The nonrestrictive example of repeating unit (R4) comprising:
--Ar °-O-Ar °-S-, as
-Ar °-S (=O)
2-Ar °-S-, as
-Ar °-C (=O)-Ar °-S-, as
And their mixture, wherein this diradical D is respectively the diradical of oxygen base, sulfonyl or phosphinylidyne.
When this poly-((arylene sulfide)) do not contain repeating unit except that repeating unit (R2), obtained good result.When being, this poly-((arylene sulfide)) when not containing poly-(phenylene sulfide) of the repeating unit except that repeating unit (R3), obtained extraordinary result.Do not contain when removing unsubstituted poly-(phenylene sulfide) to the repeating unit the phenylene repeating unit when this poly-((arylene sulfide)) is, can obtain the result of excellence.
Poly-((arylene sulfide)) is from commercially available such as the source of Chevron Phillips Chemical Company, Fortron Industries and GE Plastics.The class of trade of poly-((arylene sulfide)) class comprises
And
Poly-(phenylene sulfide) class.
According to discussed above, poly-((arylene sulfide)) (P2) can be in the form of straight-chain polymer, branched chain polymer and/or cross-linked polymer.
Polymkeric substance (P2) is with respect to the gravimetric value of the gross weight of this polymer composition 10wt.% at least preferably, and is more preferably 15wt.% at least; In addition, polymkeric substance (P2) is more preferably maximum 40wt.% with respect to the gravimetric value of the gross weight of this polymer composition 50wt.% at most preferably, also will be more preferably maximum 30wt.% and most preferably is maximum 20wt.%.
The optional composition of polymer composition
According to polymer composition of the present invention can not contain except that poly-(aryl ether ketone) (P1) and poly-((arylene sulfide)) other polymkeric substance (P2).Alternately, can comprise according to polymer composition of the present invention and be different from (P1) and a kind of terpolymer (P3) (P2); For example, by at least a poly-(aryl ether ketone) (P1), at least a poly-((arylene sulfide)) (P2) and the ternary blends that is different from (P1) and the formation of a kind of terpolymer (P3) (P2) also within the scope of the invention, prerequisite be based in this polymer composition poly-(aryl ether ketone) (P1), poly-((arylene sulfide)) (P2) and the combined weight of terpolymer (P3), the weight package of this terpolymer (P3) be contained in 0 and 25wt.% between.
Can further comprise one or more conventional additives according to polymer composition of the present invention, its value is can not be harmful to the characteristic according to polymer composition of the present invention.As the non-limitative example of examples of such additives, this can mention antioxidant, thermo-stabilizer class, anti UV agent class, fire retardant class, static inhibitor class, lubricant class, corrosion inhibitor class, pigment class, softening agent class, processing aid class, the reagent class that is used to control crosslinking degree, crosslinking accelerator class, and the like.
In a preferred embodiment of the invention, this polymer composition further comprises at least a antifriction additive.This polymer composition may further include a kind of and only a kind of antifriction additive; Alternately, this at least a antifriction additive mixture that can be at least two kinds of antifriction additives.
Then, described preferred embodiment relate in one aspect to a kind of article, these article comprise at least one part with an area supported, described part be by comprise at least a poly-(aryl ether ketone) (P1), at least a poly-((arylene sulfide)) (P2) and the polymer composition of at least a antifriction additive constitute, wherein:
-this poly-(aryl ether ketone) (P1) and should poly-((arylene sulfide)) combined weight (P2) be to be lower than 0.75 based on the gross weight of this polymer composition, and
-poly-((arylene sulfide)) (P2) with should gather (aryl ether ketone) weight ratio (P1) and be included between 0.2 and 0.8.
Described preferred embodiment also relate to a kind of polymer composition on the other hand, this polymer composition is suitable for making a kind of part with an area supported of article especially goodly, described polymer composition comprise at least a poly-(aryl ether ketone) (P1), at least a poly-((arylene sulfide)) (P2) and at least a antifriction additive, wherein:
-this poly-(aryl ether ketone) (P1) and should poly-((arylene sulfide)) combined weight (P2) be to be lower than 0.75 based on the gross weight of this polymer composition, and
-poly-((arylene sulfide)) (P2) with should gather (aryl ether ketone) weight ratio (P1) and be included between 0.2 and 0.8.
Antifriction additive
According to the present invention, a kind of " antifriction additive " is intended to represent a kind of potential component of this polymer composition, and this component provides the frictional coefficient that reduces with the polymer composition that the comparable polymer composition that does not comprise this antifriction additive is in a ratio of gained.Therefore, this antifriction additive makes the polymer composition of this gained and comprises that the article of described polymer composition have more sliding or soft and smooth or slick sensation, have this polymer composition article of described polymer composition (or comprise) with will and the material that contacts of this polymer composition between the friction that reduces.
Antifriction additive preferentially is selected from down group, it constitutes: the fluoropolymer class, and such as poly-(tetrafluoroethylene), carbon fiber, inorganic fibre, polymer fiber, graphite, silicone oil, types of silicone polymers, molybdenumdisulphide, boron nitride, silicon carbide, silica, silicon nitride, zirconium white, aluminum oxide and their mixture.It more preferably is selected from down group, and it constitutes: fluoropolymer class, carbon fiber, polymer fiber, graphite and their mixture.
In some preferred embodiment, this antifriction additive can be a kind of fine-particle solid type antifriction additive, this additive can or (that is, wherein average grain has the dimension of at least one length under 200nm) microcosmic or the nano level dimension.Term " fine-particle solid " is intended to a kind of solid that expression has non-fibrous morphology (for example ball, wafer, bar, granule, rough powder, ultrafine powder or the like) at this, or by pulverizing a kind of fine-particle solid that (that is, for example being decreased to very little particle by grinding, grind, smash to pieces or wearing and tearing) a kind of filamentary material obtains.
In the many application of ask for something, as the particle type antifriction additive, graphite is preferred.
In some other preferred embodiment, this antifriction additive can be the fortifying fibre that lubricates." fiber " as used herein and " fibrous material " are meant a kind of basic form of solid (often being crystalline), it is characterized by high relatively toughness and extremely high length-to-diameter ratio.These fibers can be successive, discontinuous, that grind, that mince and their combination.
In the many application of ask for something, as lubricated fortifying fibre, carbon fiber is preferred.
To the useful carbon fiber of the present invention can be advantageously by different polymer precursors (for example as regenerated fiber, polyacrylonitrile (PAN), aromatic polymeric amide or resol) being heat-treated and pyrolysis obtains; The carbon fiber useful to the present invention can also obtain from bituminous material.Term " graphite fibre " is intended to expression by carbon fiber being carried out the carbon fiber that high temperature pyrolysis (above 2000 ℃) obtains, and wherein carbon atom is arranged in the mode that is similar to graphite-structure.The carbon fiber useful to the present invention preferentially is selected from down group, and it constitutes: PAN base carbon fibre, asphalt base carbon fiber, graphite fibre and their mixture.
Carbon fiber is the PAN base carbon fibre preferably.The example that is suitable for use in this based carbon fiber among the present invention that has been found that comprises carbon fiber
219 grades.
Also in some other preferred embodiment, the article that have an area supported comprise the mixture of at least two kinds of antifriction additives.
The mixture of at least two kinds of antifriction additives is preferably by at least a antifriction additive that is selected from fine-particle solid type antifriction additive, and is selected from that at least a other antifriction additives of lubricated fortifying fibre form.
A kind of first preferred mixture is the blend of carbon fiber and graphite.Also will be more preferably, it is the blend of graphited asphalt base carbon fiber and graphite.The weight ratio of carbon fiber and graphite advantageously at least 1, preferably at least 1.5 and more preferably at least 1.75.On the other hand, the weight ratio of carbon fiber and graphite advantageously maximum 3, preferred maximum 2.5 and more preferably maximum 2.25.
Another kind of preferred mixture is the blend of carbon fiber and poly-(tetrafluoroethylene).Also will be more preferably, it is the blend of graphited asphalt base carbon fiber and poly-(tetrafluoroethylene).The weight ratio of this carbon fiber and poly-(tetrafluoroethylene) advantageously at least 1, preferably at least 1.5 and more preferably at least 1.75.On the other hand, the weight ratio advantageously maximum 3, preferably maximum 2.5 of this carbon fiber and poly-(tetrafluoroethylene) and be more preferably maximum 2.25.
The weight ratio of this antifriction additive and polymer composition normally is lower than 0.70, and is preferably maximum 0.6, is more preferably maximum 0.55 and will be more preferably maximum 0.50.On the other hand, the weight ratio of this antifriction additive and polymer composition is advantageously minimum 0.10, or even at least 0.20, or even greater than 0.25; It is preferably at least 0.30, more preferably at least 0.35 and will be more preferably at least 0.40 years old.
In according to a particularly preferred embodiment of the present invention, this polymer composition basically by or or even by at least a poly-(aryl ether ketone) (P1), at least a poly-((arylene sulfide)) (P2) and at least a antifriction additive form, wherein:
The weight of-this antifriction additive based on the gross weight of this polymer composition, is greater than 0.25, preferably at least 0.30, be more preferably at least 0.35 and will be more preferably at least 0.40, and
-poly-((arylene sulfide)) (P2) with gather (aryl ether ketone) weight ratio (P21) and be included between 0.2 and 0.8.
The gravimetric value that is included in the polymer composition in the part of the article that have an area supported is with respect to the gross weight of described part 10wt.% at least advantageously, and preferably 50wt.% at least is more preferably 80wt.% at least.Also will be more preferably, described part is made of polymer composition of the present invention basically.
The component of polymer composition of the present invention, particularly polymkeric substance (P1), polymkeric substance (P2), optional polymkeric substance (P3) and optional one or more antifriction additives can be blend or mediate.For example, all components of this polymer composition at first can be carried out blend and then carry out coextrusion.Alternately, these components can use different feed zone to be fed to forcing machine respectively at last.If need, can and be fed to this forcing machine subsequently to the blend more in advance in them.For example, can carry out blend and be fed in the forcing machine to mediate these one or more antifriction additives (together or respectively) subsequently these polymeric constituents [polymkeric substance (P1)+polymkeric substance (P2)] can be in fed downstream.
Generally, the described part that has article of an area supported has the outstanding balance of tribological property and mechanical property, significant dimensional stability, chemical resistance, excellent surface smoothness (for example glossiness smooth-flat-surface) and strict size precision.Because characteristic mentioned above, show especially usually in the framework that secular friction and wear is used according to article of the present invention and can stand the harsh working conditions (environment of for example low-down or very high use temperature, rodent chemical environment, exsiccant or liquid; At a high speed; Low speed; High-load; Unusual Chang duration of service; The PV that improves; Or the like).
Advantageously, article according to the present invention are used as slipper, in particular as the slipper in friction and wear is used.
Described article include but not limited to following article, all like supporting member classes that high relatively load, high relatively speed or both stand that stands." supporting member " as used herein and " supporting member class " be meant have one in relative movement with a surface interaction (for example by slide, pivot, swing, back and forth, rotation or like that) any or multiple article on surface.The example of these type of article includes but not limited to the packing ring and the dynamic packing ring of bearing, axle bush, gear, sleeve bearing, sealing-ring, shaft bearing, thrust washer, rubbing strip, sliding part, bearing gasket, spot contact bearing (comprising ball), valve seat, piston ring, valve guiding piece, compressor blade, sealing member, static state and requires in other application of wear-resistant and self-lubricating.
Preferentially be selected from supporting member class, antifriction bearing cage, thrust washer, brush packing ring, axle bush, sealing-ring, sliding part, cable support, spot contact bearing ball, cam follower and the gear that comprises the metal-polymer bearing according to article of the present invention.
In a specific embodiments, the CMP retaining ring that article according to the present invention are a kind of chemical-mechanical planarization effects, this retaining ring comprise at least one part with an area supported, and this part is to be made of polymer composition as described above.This CMP retaining ring by exhaustive be described in the U.S. Provisional Application of submitting on April 23rd, 2007 before quoted number 60/913,395.This CMP retaining ring can be in the form of annular ring.This CMP retaining ring can have with the contacted top of substrate carrier and with the contacted bottom of substrate, wherein this top is to be made by the material of the polymer composition that is different from the bottom.Whole retaining ring can be made by this polymer composition.This retaining ring can be in and have the not form of the angle ring of closed circumference.This retaining ring can have upper section or the part that comprises a kind of metal.
The CMP method comprises generally: the surface of a wafer is contacted with a polishing pad simultaneously this wafer is remained in the substrate carrier that comprises retaining ring as described above, and at least one rotation that makes simultaneously in this substrate carrier and this polishing pad is polished on the surface of this wafer, and wherein this maintenance is undertaken by this retaining ring is contacted with this wafer.The surface of this wafer can contact with a polishing pad in the presence of a kind of polishing material.The surface of this wafer can contact in the presence of the aqueous mixture that comprises a kind of colloidal silica with polishing pad.This matrix can be a kind of silicon wafer; This silicon wafer can have circular shape and in polishing process this wafer swim in the zone that limits by retaining ring.
This substrate carrier comprises generally: CMP retaining ring, a backing spare and a body as described above, wherein this retaining ring is extendible and telescopic and this retaining ring is extended with one and/or constriction device is connected to this body from this body.The body of this substrate carrier can be rotatable.
The present invention still has at least a poly-((arylene sulfide)) that relate to a significant quantity (ε) on the other hand (P2) to be used for diluting at least a poly-(aryl ether ketone) purposes (P1) that is included in a kind of polymer composition, and simultaneously the rub resistance of this polymer composition and/or wear resistance is maintained at least and comprise this poly-(aryl ether ketone) and (P1), do not contain this poly-essentially identical level of ((arylene sulfide)) polymer composition (P2).Should poly-((arylene sulfide)) significant quantity (ε) (P2) (P1) advantageously be lower than 50wt.% with poly-((arylene sulfide)) combined weight (P2) based on poly-(aryl ether ketone) in this polymer composition, preferably be lower than 40wt.%, and more preferably less than 35wt.%.In addition, ε based on poly-(aryl ether ketone) in this polymer composition (P1) and poly-((arylene sulfide)) combined weight (P2) advantageously on 15wt.%, preferably on the 25wt.% and more preferably on 30wt.%.
Illustrative example of the present invention below is provided, but has not limited it.
Example
Two kinds of polymer compositions produced according to the present invention, i.e. polymer composition E1 and E2.The another kind of polymer composition relative, i.e. polymer composition CE1 have also been prepared in order to contrast with the present invention.In table 1, listed the property quality and quantity of all the components that is included in the exemplary polymer composition.
Poly-(aryl ether ketone) that in these experiments, uses (PEEK) and poly-((arylene sulfide)) be respectively (PPS) from Solvay Advanced Polymers, L.L.C's
KT-880P and by the T-4G of the DIC grade of Dainippon Ink and Chemicals supply; The PAN base carbon fibre is from Toho Tenax America, and Inc. buys
219, and the superior class 4 735FF of Graphite Powder 99 buys from Superior Graphite.
Table 1
Prescription (wt.%)
| ??E1 | ??E2 | ??CE1 | |
| ??PEEK | ??36.7 | ??36.7 | ??55 |
| ??PPS | ??18.3 | ??18.3 | ??- |
| Carbon fiber | ??30 | ??30 | ??30 |
| ??PTFE | ??15 | ??- | ??15 |
| Graphite | ??- | ??15 | ??- |
Preparation condition
The prescription of example and contrast is prepared on the engagement type twin screw extruder in the same way at a Berstorff25mm, and this forcing machine is to be constituted and had a L of 40: 1 by eight machine barrel districts: the ratio of D.Carbon fiber is fed to this forcing machine by a side feed appliance with the gravimetric analysis mode at machine barrel 5, and all the other compositions of this prescription are reversed blend in each case and at machine barrel 1 place with the charging of gravimetry mode.Use vacuum ventilation to remove any moisture or other volatile matters of the melts before having thigh and granulating of one's own at machine barrel 7 places.These strands are by cooling off in the immersion tank and be transported to then on the personal share material platform (strand table), on this platform these thighs being carried out air cooling granulating then subsequently.In table 2, illustrated at the preparation example with to setting and other conditions of employed barrel zone temperature in the same old way.
Table 2
Be used to prepare sample E1, E2 and to the preparation operating parameter of CE1 in the same old way
| Setting point | |
| Machine barrel 1 temperature (℃) | Do not heat |
| Machine barrel 2 temperature (℃) | ??330 |
| Machine barrel 3 temperature (℃) | ??330 |
| Machine barrel 4 temperature (℃) | ??330 |
| Machine barrel 5 temperature (℃) | ??330 |
| Machine barrel 6 temperature (℃) | ??340 |
| Machine barrel 7 temperature (℃) | ??340 |
| Machine barrel 8 temperature (℃) | ??340 |
| The die orifice adapter (℃) | ??340 |
| Die orifice (℃) | ??330 |
| Melt temperature (℃) | ??385-395 |
| Screw speed (RPM) | ??220 |
| Vacuum (in Hg) | ??27 |
| Feeding rate, carbon fiber (lb/hr) | ??6 |
| Feeding rate, other compositions (lb/hr) | ??14 |
| Total treatment rate (lb/hr) | ??20 |
Will be by sample of pellets dried overnight (about 16 hours) in the exsiccant convection oven of the temperature that is set at 300 ° (149 ℃) of process production described above.Use 50 tons the Sumitomo injection molding press (maximum hydraulic pressure pressure is 2180 pounds/square inch) of standard to contrast then and the exsiccant pellet of example carries out injection molding to provide the thrust washer specimen.Molding temperature is provided with condition and is summarized in the table 3.
Table 3
Molded condition
Wear resistance is measured
The friction and wear test is to use the thrust washer sample of Falex Multispecimen test molding machine to carry out.This sample geometrical shape and test are carried out according to ASTM D3702.Wear resistance measuring result for E1, E2 and CE1 provides in table 4.
Table 4
(x 10 for the wear factor result
-10In
3-min/ft-lb-hr)
| ??E1 | ??E2 | ??CE1 | |
| (75 feet per minutes, 1000 pounds/square inch) that lubricate | ??3.4 | ??2.7 | ??2.9 |
In a kind of beat all mode, blend of the present invention (E1 and E2) has been realized wear factor is maintained and the polymer composition relative with the present invention essentially identical level of wear factor of (not containing any PPS (CE1)).Blend E2 of the present invention compares with the wear resistance of case of comparative examples (CE1) even reaches the level that has improved wear resistance.
Obviously, in view of the above content of teaching, multiple modification and the change that might make the present invention.Therefore it should be understood that within the scope of appended claim, can be by implementing the present invention except that other modes this is specifically described.
Claims (15)
1. article, it comprises at least one parts with area supported, described parts by comprise at least a poly-(aryl ether ketone) (P1) and at least a poly-((arylene sulfide)) polymer composition (P2) form, wherein:
_ based on the gross weight meter of described polymer composition, described poly-(aryl ether ketone) (P1) and described poly-((arylene sulfide)) combined weight (P2) for be lower than 0.75 and
_ described poly-((arylene sulfide)) (P2) is included between 0.2 and 0.8 with described (aryl ether ketone) weight ratio (P1) of gathering.
2. article according to claim 1, wherein said poly-(aryl ether ketone) are that poly-(ether ether ketone) and described poly-((arylene sulfide)) are poly-(phenylene sulfide) (P2) (P1).
3. article according to claim 1 and 2, wherein said polymer composition further comprises at least a antifriction additive.
4. article according to claim 3, the weight ratio of wherein said antifriction additive and polymer composition is at least 0.30.
5. article according to claim 4, wherein based on the gross weight meter of described polymer composition, described poly-(aryl ether ketone) (P1) and described poly-((arylene sulfide)) combined weight (P2) at least 0.40 and the weight ratio of described antifriction interpolation and polymer composition be at least 0.40.
6. according to each described article in the claim 3 to 5, wherein said antifriction additive is selected from fluoropolymer, carbon fiber, polymer fiber, graphite and their mixture.
7. article according to claim 6, the mixture of wherein said antifriction additive or carbon fiber and graphite, or the mixture of carbon fiber and poly-(tetrafluoroethylene), wherein respectively, the scope of the weight ratio of the weight ratio of described carbon fiber and graphite or described carbon fiber and poly-(tetrafluoroethylene) is between 1.75 and 2.25.
8. according to each described article in the above claim, wherein said poly-((arylene sulfide)) is from 0.3 to 0.7 with the scope of gathering (aryl ether ketone) weight ratio (P1) (P2).
9. article according to claim 8, wherein said poly-((arylene sulfide)) are from 0.4 to 0.6 with the scope of gathering (aryl ether ketone) weight ratio (P1) (P2).
10. according to each described article in the above claim, it is selected from the packing ring and the dynamic packing ring of bearing, axle bush, gear, sleeve bearing, sealing-ring, shaft bearing, thrust washer, rubbing strip, sliding part, bearing gasket, spot contact bearing, valve seat, piston ring, valve guiding piece, compressor blade, sealing member, static state.
11. according to each described article in the claim 1 to 9, described article are retaining rings of chemical-mechanical planarization.
12. a polymer composition, described composition are suitable for making the parts with area supported of article especially goodly, described polymer composition comprises that at least a poly-(aryl ether ketone) (P1) gathers ((arylene sulfide)) (P2) with at least a, wherein:
_ based on the gross weight meter of described polymer composition, described poly-(aryl ether ketone) (P1) and described poly-((arylene sulfide)) combined weight (P2) for be lower than 0.75 and
_ described poly-((arylene sulfide)) (P2) is included between 0.2 and 0.8 with described (aryl ether ketone) weight ratio (P1) of gathering.
13. polymer composition according to claim 12, wherein said polymer composition further comprises at least a antifriction additive, and the weight ratio of this antifriction additive and polymer composition is at least 0.30.
14. according to claim 12 or 13 described article, wherein:
_ described poly-(aryl ether ketone) is that poly-(ether ether ketone) and described poly-((arylene sulfide)) are poly-(phenylene sulfide) (P2) (P1),
_ based on the gross weight meter of described polymer composition, described poly-(aryl ether ketone) (P1) and described poly-((arylene sulfide)) combined weight (P2) at least 0.40 and
_ described poly-((arylene sulfide)) is from 0.3 to 0.7 with described scope of gathering (aryl ether ketone) weight ratio (P1) (P2).
15. at least a poly-((arylene sulfide)) of significant quantity (ε) (P2) is used for diluting at least a poly-(aryl ether ketone) purposes (P1) that is included in polymer composition, wherein simultaneously the rub resistance of described polymer composition and/or wear resistance maintained at least and comprises rub resistance and/or the essentially identical level of wear resistance that described poly-(aryl ether ketone) (P1), do not contain described poly-((arylene sulfide)) polymer composition (P2).
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| US60/915,973 | 2007-05-04 | ||
| PCT/EP2008/054918 WO2008129059A1 (en) | 2007-04-23 | 2008-04-23 | Friction and wear resistant articles |
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| CN101679741A true CN101679741A (en) | 2010-03-24 |
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| CN200880013334.5A Active CN101668814B (en) | 2007-04-23 | 2008-04-23 | Thermoplastic polymer mixtures, and applications thereof |
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| EP (2) | EP2142599B1 (en) |
| JP (1) | JP5621172B2 (en) |
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- 2008-04-23 WO PCT/EP2008/054954 patent/WO2008116939A2/en active Application Filing
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105189654A (en) * | 2012-11-09 | 2015-12-23 | 索尔维特殊聚合物美国有限责任公司 | PAEK/PAES compositions |
| CN105189654B (en) * | 2012-11-09 | 2017-12-19 | 索尔维特殊聚合物美国有限责任公司 | PAEK/PAES compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2008116939A3 (en) | 2008-11-27 |
| WO2008116939A2 (en) | 2008-10-02 |
| EP2142600A2 (en) | 2010-01-13 |
| JP2010525126A (en) | 2010-07-22 |
| CN101668814B (en) | 2012-08-08 |
| EP2142599A1 (en) | 2010-01-13 |
| JP5621172B2 (en) | 2014-11-05 |
| WO2008129059A1 (en) | 2008-10-30 |
| EP2142600B1 (en) | 2014-07-23 |
| CN101668814A (en) | 2010-03-10 |
| US9000087B2 (en) | 2015-04-07 |
| US20100144955A1 (en) | 2010-06-10 |
| EP2142599B1 (en) | 2016-12-14 |
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